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Study of the Effects of Substitution on the Absorption Spectra of Porphin
Abstract
A model is presented for the excited states of porphin, which are viewed as arising from two configurations which can be mixed to varying degrees. The effects of substituents are then discussed, first the limitations imposed by symmetry requirements and then the requirements imposed if they act as one electron perturbations. The theory is applied to certain experimental problems. First it is shown how the metal porphins can be viewed as a series showing increasing mixing of the two fundamental configurations. Next the effect of free base formation is explained as a cyclic polyene perturbation. This theory predicts that the lowest porphin transition is polarized parallel to the H–H axis. Formulas are derived for intensity changes caused by various external substituents; their effect on transition energies are also discussed. Finally formulas are developed to account for the effects of aza substitution on the methine bridges.
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Cited by
Mathew, S., Yella, A., Gao, P., Humphry-Baker, R., Curchod, B. F. E., Ashari-Astani, N., Tavernelli, I., Rothlisberger, U., Nazeeruddin, M. K., & Grätzel, M. (2014) · Nature Chemistry · doi:10.1038/nchem.1861 · Cited by 4,473
Efficient Light Harvesting by Using Green Zn-Porphyrin-Sensitized Nanocrystalline TiO2 Films
Wang, Q., Campbell, W. M., Bonfantani, E. E., Jolley, K. W., Officer, D. L., Walsh, P. J., Gordon, K., Humphry-Baker, R., Nazeeruddin, M. K., & Grätzel, M. (2005) · The Journal of Physical Chemistry B · doi:10.1021/jp052877w · Cited by 438
New perspectives in multireference perturbation theory: the n-electron valence state approach
Angeli, C., Pastore, M., & Cimiraglia, R. (2007) · Theoretical Chemistry Accounts · doi:10.1007/s00214-006-0207-0 · Cited by 281
Perlík, V., Seibt, J., Cranston, L. J., Cogdell, R. J., Lincoln, C. N., Savolainen, J., Šanda, F., Mančal, T., & Hauer, J. (2015) · The Journal of Chemical Physics · doi:10.1063/1.4919548 · Cited by 56
Metadata
- Authors
- Gouterman, M.
- Venue
- The Journal of Chemical Physics
- Publisher
- AIP Publishing
- Published
- 1959-05-01
- Volume
- 30
- Issue
- 5
- Pages
- 1139-1161
- ISSN
- 0021-9606 (ISSN-L)
- 1089-7690
- OpenAlex
- W1975798543
- Cited by
- 1,001
- References
- 0
- FWCI
- 5.85
- Type
- journal article
- Language
- en
- Open access
- closed
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- Gouterman, M. (1959). Study of the Effects of Substitution on the Absorption Spectra of Porphin. The Journal of Chemical Physics. https://doi.org/10.1063/1.1730148
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Contains information from the Semantic Scholar Academic Graph Datasets, made available under the ODC Attribution License (ODC-BY 1.0).
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